CN114262901B - Application of cuprous bromide in electrocatalytic decomposition of water - Google Patents
Application of cuprous bromide in electrocatalytic decomposition of water Download PDFInfo
- Publication number
- CN114262901B CN114262901B CN202111626682.3A CN202111626682A CN114262901B CN 114262901 B CN114262901 B CN 114262901B CN 202111626682 A CN202111626682 A CN 202111626682A CN 114262901 B CN114262901 B CN 114262901B
- Authority
- CN
- China
- Prior art keywords
- cuprous bromide
- nanorod
- application
- copper
- heat treatment
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Classifications
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Abstract
The application discloses the application of cuprous bromide in electrocatalytic decomposition of water for the first time, and shows excellent catalytic hydrogen production performance. The method mainly influences the formation of cuprous bromide on the surface of the copper hydroxide nanorod by halogen in the heat treatment process, and can form a cuprous bromide nanorod structure at a proper temperature. After the preliminary liquid phase synthesis of copper hydroxide nanorods, a bromine source is introduced to complete a bromination reaction by a tube furnace heat treatment method, and the hydrogen production performance of the material after decomposing water is tested under an alkaline condition. The application successfully synthesizes a cuprous bromide nanorod, invents an electrocatalytic hydrogen production electrode with good intrinsic catalytic performance, and is the first application of the material for electrocatalytic hydrogen production.
Description
Technical Field
The application belongs to the field of clean sustainable novel energy preparation and application, and particularly relates to application of cuprous bromide in electrocatalytic decomposition of water.
Background
The gradual exhaustion of traditional fossil energy is urgent to promote human beings to develop efficient sustainable novel clean energy. Among various alternative energy sources, hydrogen energy is considered as one of the energy sources having great potential for use, and electrolyzed water of cathodic Hydrogen Evolution (HER), which is one of important sources of hydrogen energy, has thus received attention. However, currently commercial HER electrocatalysts are platinum-based precious metal materials, with a relatively high cost of raw materials. Moreover, recent studies indicate that such electrocatalysts have poor stability for long term operation in strong acid or alkaline environments.
In recent years, efforts have been made to find inexpensive, stable, and abundant electrocatalytic materials, such as transition metal carbides, sulfides, borides, nitrides, phosphides, and the like. In the reported related literature, mostly single metal compounds are dominant, and are mutually regulated with other nonmetal, metal and heterogeneous materials to improve the surface electronic state or regulate the surface morphology so as to improve the electrocatalytic activity. However, the current work has a low degree of expansion for the rest of the system, and the combination with transition metals is concentrated only between the small amounts of non-metallic elements. Therefore, the other nonmetallic compound systems are actively expanded, and the search of the high intrinsic electrocatalytically active electrode material has important scientific significance for the research of HER.
The existing copper-based compounds have certain defects in the process of decomposing water, such as: the adsorption of active hydrogen is stronger, so that the desorption of bubbles is slower, and the catalytic activity is low; unreasonable structure, poor stability, etc. The application solves the bottleneck problem of catalytic activity from the two angles of morphology and intrinsic activity, accurately synthesizes complex nanotopography, increases the active area of catalytic reaction, develops a new bromide system to improve the intrinsic electron distribution of the material, optimizes the overpotential of the copper-based compound in the HER process, greatly improves the water electrocatalytic decomposition performance of the copper-based compound, and promotes the application of cuprous bromide series materials in industrial catalysis.
Disclosure of Invention
Aiming at the defects of the prior art, the application provides a cuprous bromide material with high catalytic activity, which is the first time used for preparing hydrogen by high-efficiency electrocatalytic decomposition of water.
Traditionally, cuprous bromide materials are often used as coupling catalysts in organic reactions because of the large number of active bromine free radicals generated by decomposition of the cuprous bromide materials; the use of cuprous bromide in the field of photocatalysis has also been reported only rarely because of its narrower band gap. The key point of the hydrogen production by the electrocatalytic decomposition of water in the alkaline electrolyte is that electrons are continuously and efficiently transferred from oxygen anions to hydrogen cations, however, due to the existence of cuprous ions, the traditional cuprous bromide material is easy to oxidize in a liquid environment and has insufficient stability, so that the application in the field of electrocatalytic decomposition of water has not been reported. The cuprous bromide material has a cubic phase CuBr with a nano rod-shaped structure based on self-supporting in-situ growth on the foamy copper, on one hand, bromine has larger electronegativity as an active site,the electron transfer process is easy to be guided, and the typical centering reaction (Cu+Cu) between different valence states of copper element is adopted 2+ ＝2Cu + ) The cuprous bromide growing on the foamy copper is not easy to oxidize, and the catalytic stability of the cuprous bromide is greatly improved. On the other hand, the nanoscale structure provides a large amount of catalytic reaction area, so that the catalytic efficiency is further improved compared with CuBr bulk materials, and finally, the overpotential of the electrocatalytic hydrogen production reaction is greatly reduced.
Further, the rod-like structure catalyzes the formation of H 2 The desorption of bubbles is more facilitated, the bubbles are prevented from blocking the active sites, and the continuous proceeding of the catalytic reaction is facilitated. Therefore, the product greatly improves the catalytic activity from the aspects of morphology construction and intrinsic activity.
The application also provides a preparation method of the cuprous bromide nanorod for the first time, which mainly promotes bromine in Cu (OH) by the decomposition of hexabromobenzene by heating in the heat treatment process 2 Surface chemical combination can form optimal phase components at proper synthesis temperature, and the surface morphology is a nano rod structure.
Specifically, the copper hydroxide nanorod-shaped structural material is placed at the downstream of a tube furnace, hexabromobenzene (HBB) powder tabletting is carried out at the upstream, argon is used as carrier gas, the temperature is 350-550 ℃ for heat treatment for 2 hours, and the copper hydroxide nanorod-shaped structural material is naturally cooled to room temperature and taken out, so that the cuprous bromide nanorod-shaped structural material is obtained.
Further, the copper hydroxide nanorod-shaped structural material with the foam copper as a framework is prepared by the following method: ultrasonic cleaning copper foam sequentially with acetone, 4M hydrochloric acid, deionized water and ethanol, drying with Ar gas at high speed, and placing in a solution containing precursor (120 mmol NaOH and 6mmol (NH) 4 ) 2 S 2 O 8 45mL of the mixed aqueous solution) is subjected to liquid phase reaction, standing is carried out at room temperature for 30 minutes, deionized water and ethanol are used for cleaning, so that adsorbed impurities on the surface are removed, and the cuprous bromide nanorod-shaped structural material is obtained on the foam copper substrate.
The application has the advantages that: bromination is carried out through heat treatment, cuprous bromide crystals are grown on the surface of the nano rod, and the cuprous bromide crystals are formed from two angles of morphology construction and intrinsic activityGreatly improves the activity of electrocatalytic hydrogen production. The obtained 450 ℃ heat treatment product CuBr NR/CF reaches 10mA cm under alkaline condition -2 The overpotential required for the catalytic current density is only 122mV, compared with Cu (OH) 2 The overpotential of NR/CF (295 mV) at this current density was reduced by 58%. And the catalytic stability is good.
Drawings
FIG. 1 is a graph of CuBr NR/CF (example 1) and Cu (OH) prepared at optimum heat treatment temperature according to the application 2 X-ray diffraction spectra of NR/CF precursor (comparative example 1) and copper foam substrate (CF).
FIG. 2 is an X-ray diffraction spectrum of CuBr NR/CF prepared according to the present application at various heat treatment temperatures (examples 1-3).
FIG. 3 shows the preparation of CuBr NR/CF (examples 1-3) and Cu (OH) at various heat treatment temperatures according to the application 2 Scanning electron microscope image of NR/CF (comparative example 1).
FIG. 4 is an energy dispersive X-ray spectroscopy (EDS) surface elemental analysis of a CuBr NR/CF prepared in accordance with the present application at an optimal heat treatment temperature (example 1).
FIG. 5 is a chart showing the preparation of CuBr NR/CF (example 1) and Cu (OH) according to the present application 2 Electrochemical polarization curves for NR/CF (comparative example 1), cu/CF as hydrogen evolution reaction catalysts.
FIG. 6 is an electrochemical polarization curve of CuBr NR/CF (examples 1-3) as hydrogen evolution reaction catalyst prepared according to the present application at various heat treatment temperatures.
Detailed Description
The technical solution of the present application will be further described with reference to examples, which should not be construed as limiting the technical solution.
Example 1:
(1) Copper Foam (CF) is first pretreated to remove oil and oxide layers from the surface: sequentially ultrasonic cleaning with acetone, 4M hydrochloric acid, distilled water and ethanol, and drying with Ar gas high-speed air flow.
(2)Cu(OH) 2 Synthesis of NR/CF precursor: 4.8000g (120 mmol) of NaOH and 1.3692g (6 mmol) of (NH) 4 ) 2 S 2 O 8 (APS) was added to 45mL of deionized water and magnetically stirred for 10min to allow the solute to dissolve well. Then adding the pretreated foamy copper with the size of 2cm x 3cm, standing for 30 minutes, taking out, washing with deionized water and ethanol, drying with Ar gas high-speed air flow, and turning the surface of the material into light blue to obtain Cu (OH) 2 NR/CF precursor.
(3) Synthesis of CuBr NR/CF: cu (OH) 2 The NR/CF precursor is placed at the downstream of a tube furnace, the upstream is pressed into tablets with 0.3g of Hexabromobenzene (HBB) powder, the carrier gas is argon, the heat treatment is carried out for 2 hours at 450 ℃ (the heating speed is 10 ℃/min), and the mixture is naturally cooled to room temperature and taken out.
Example 2: the difference from example 1 is that: the heat treatment temperature was changed to 350 ℃.
Example 3: the difference from example 1 is that: the heat treatment temperature was changed to 550 ℃.
Comparative example 1:
(1) The copper foam is first pretreated to remove oil and oxide layers from the surface: sequentially ultrasonic cleaning with acetone, 4M hydrochloric acid, distilled water and ethanol, and drying with Ar gas high-speed air flow.
(2)Cu(OH) 2 Synthesis of NR/CF precursor: 4.8000g (120 mmol) of NaOH and 1.3692g (6 mmol) of (NH) 4 ) 2 S 2 O 8 (APS) was added to 45mL of deionized water and magnetically stirred for 10min to allow the solute to dissolve well. Then adding the pretreated foamy copper with the size of 2cm x 3cm, standing for 30 minutes, taking out, washing with deionized water and ethanol, drying with Ar gas high-speed air flow, and turning the surface of the material into light blue to obtain Cu (OH) 2 NR/CF precursor.
FIG. 1 is a heat treatment of CuBr NR/CF (example 1) with Cu (OH) at 450 ℃ 2 The X-ray diffraction spectra of the NR/CF precursor (comparative example 1) and Cu/CF substrate can be seen to show that CuBr NR/CF is a single cubic phase CuBr (PDF # 82-2118) except for the copper foam substrate, with peaks of 2 theta at 27.09 DEG, 44.98 DEG, 53.30 DEG, 65.50 DEG, and 72.24 DEG corresponding to the (111), (220), (311), (400), and (331) crystal planes of cubic CuBr, respectively.
FIG. 2 is an X-ray diffraction spectrum of 450℃heat treated CuBr NR/CF (example 1) and 350℃heat treated CuBr NR/CF (example 2) and 550℃heat treated CuBr NR/CF (example 3). At a treatment temperature of 350 c (example 2), bromination was weaker and only a small amount of cuprous bromide was formed. As the temperature increases, the hexabromobenzene is completely decomposed, the cuprous bromide content increases, and the cuprous bromide crystalline phase content is highest at the treatment temperature of 450 ℃ (example 1). The disruption of the crystal structure portion at 550 c treatment temperature (example 3) by high temperature, such as heat treatment at higher temperature, will lead to a gradual trend of the system toward the amorphous state.
FIG. 3 is a scanning electron microscope image of a prepared CuBr NR/CF at different heat treatment temperatures. As can be seen, cuBr NR/CF inherits Cu (OH) 2 The nanorod-like structure of the NR/CF precursor (comparative example 1, panel d) had a higher surface roughness at 350 ℃ (example 2, panel a), at which time the transition to CuBr was not yet complete; the rod-like structure is most uniform under the condition of 450 ℃ (example 1, figure b), the orientation is good, and the surface is the most smooth; at 550 ℃ (example 3, panel c), the rod-like structure partially collapsed and agglomerated, but the rod-like array structure remained overall. Therefore, the appearance of the nanorod formed under the control and synthesis effect of hexabromobenzene is influenced by temperature, and the appearance collapse tends to be generated when the temperature is too high. The complex nanorod morphology provides a reaction interface and a large number of active sites for the electrocatalytic decomposition of water.
FIG. 4 is an energy dispersive X-ray spectroscopy surface element analysis of a 450℃heat treated CuBr NR/CF prepared in accordance with the present application (example 1). It can be seen that bromine elements are uniformly distributed on the nanorods, a small amount of carbon exists in the system, the element contents (wt%) of Cu, br and C are 40.16%, 37.25% and 22.58%, respectively, corresponding to the bromine element contents in the samples of the heat treatment CuBr NR/CF at 350 ℃ and the heat treatment CuBr NR/CF at 550 ℃ respectively being 30.28wt% and 44.87wt%, however, the crystal phase containing carbon is not analyzed in XRD, which indicates that the carbon element is electrostatically adsorbed on the surface of the material in an amorphous form after the decomposition of hexabromobenzene.
FIG. 5 is a 450 ℃ heat treatment of CuBr NR/CF (example 1) with pure phase copper foam and precursor Cu (OH) prepared according to the application 2 NR/CF (comparative example 1)Is the electrochemical polarization curve of the hydrogen evolution reaction catalyst. HER testing was performed using CuBr NR/CF as the cathode and argon saturated 1M KOH as the electrolyte. As shown in FIG. 3, compared with copper foam and Cu (OH) 2 NR/CF, cuBr NR/CF has obvious hydrogen evolution catalytic activity, reaching 10mA/cm 2 The overpotential was only 122mV, compared to Cu (OH) 2 NR/CF (294 mV) was reduced by 58%;100mA/cm 2 The overpotential is only 250mV at the current density of (c).
FIG. 6 is an electrochemical polarization curve of the prepared CuBr NR/CF (examples 1-3) of the present application at various temperatures as hydrogen evolution reaction catalysts. HER testing was performed using CuBr NR/CF as the cathode and argon saturated 1M KOH as the electrolyte. As can be seen, the CuBr NR/CF prepared at different temperatures all showed significant electrocatalytic activity (examples 1 to 3 at 10mA/cm 2 The overpotential was only 122mV,147mv and 152mV, respectively), wherein the CuBr phase formed the best 450 ℃ treatment sample corresponding to the most excellent catalytic activity, demonstrating the superior intrinsic catalytic activity of cubic CuBr (PDF # 82-2118).
Because the traditional cuprous bromide material is easy to oxidize in a liquid environment and has insufficient stability, the application does not set a comparative example for performance comparison.
The application realizes the halogen regulation synthesis method of the cuprous bromide nanorod and applies the method to the electrocatalytic decomposition of water, and obtains better catalytic performance by keeping good intrinsic catalytic activity and surface morphology with excellent structure. The high catalytic activity, stability, easy synthesis and low cost of the cuprous bromide nanorods indicate that the transition metal bromide can be further developed and researched as a novel electrocatalytic material system to promote the further application of the transition metal bromide in the field of water decomposition.
Claims (4)
1. The application of cuprous bromide as hydrogen evolution reaction catalyst in electrocatalytic decomposition water is characterized in that: the nano rod-shaped structure based on self-supporting in-situ growth on the foamy copper has a cubic phase crystal phase, and the bromine content is 30-45 wt%, and the preparation method comprises the following steps: and (3) obtaining a copper hydroxide nanorod-shaped structural material on the foam copper substrate, placing the copper hydroxide nanorod-shaped structural material at the downstream of a tube furnace, tabletting hexabromobenzene powder at the upstream of the tube furnace, carrying out heat treatment for 2 hours at 350-550 ℃ by using argon as carrier gas, naturally cooling to room temperature, and taking out to obtain the cuprous bromide nanorod-shaped structural material.
2. The use according to claim 1, characterized in that: the bromine content was 37.25% by weight.
3. Use according to claim 1, characterized in that the heat treatment temperature is changed to 450 ℃.
4. The use according to claim 1, wherein the copper hydroxide nanorod-like structure material is prepared by the following method: ultrasonic cleaning copper foam sequentially with acetone, 4M hydrochloric acid, deionized water and ethanol, drying with Ar gas at high speed, and placing in a container containing 120mmol NaOH and 6mmol (NH) 4 ) 2 S 2 O 8 Liquid phase reaction is carried out in a beaker of 45mL of mixed aqueous solution, standing is carried out for 30 minutes at room temperature, deionized water and ethanol are used for cleaning, so as to remove adsorbed impurities on the surface, and the copper hydroxide nanorod-shaped structural material is obtained on the foam copper substrate.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111626682.3A CN114262901B (en) | 2021-12-28 | 2021-12-28 | Application of cuprous bromide in electrocatalytic decomposition of water |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202111626682.3A CN114262901B (en) | 2021-12-28 | 2021-12-28 | Application of cuprous bromide in electrocatalytic decomposition of water |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN114262901A CN114262901A (en) | 2022-04-01 |
| CN114262901B true CN114262901B (en) | 2023-08-18 |
Family
ID=80830897
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202111626682.3A Active CN114262901B (en) | 2021-12-28 | 2021-12-28 | Application of cuprous bromide in electrocatalytic decomposition of water |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114262901B (en) |
-
2021
- 2021-12-28 CN CN202111626682.3A patent/CN114262901B/en active Active
Non-Patent Citations (1)
| Title |
|---|
| Importance of cobalt- doping for the preparation of hollow CuBr/Co@CuO nanocorals on copper foils with ehanced electeocatalytic activity and stablility for oxygen evolution reaction;CHien wei wu et. al.;《ACS sustainable chem eng》;第8卷;9794-9802 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN114262901A (en) | 2022-04-01 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Dunfeng et al. | CO 2 Reduction | |
| Chen et al. | Recent advances in the utilization of copper sulfide compounds for electrochemical CO2 reduction | |
| CN108385124B (en) | Preparation method of transition metal/carbon tube/graphene electrocatalyst for hydrogen evolution reaction | |
| CN107349937B (en) | Preparation method of graphene-based bimetallic sulfide nano composite photocatalyst | |
| CN107519905B (en) | Vanadium carbide nano-sieve electrocatalytic material capable of being used in wide pH range and preparation method thereof | |
| CN113751029B (en) | Co (cobalt) 9 S 8 /ZnIn 2 S 4 Photocatalytic hydrogen production material and preparation method and application thereof | |
| CN112058286B (en) | In-situ preparation method of two-dimensional Prussian blue analogue @ MXene composite electrocatalyst | |
| CN111905767B (en) | Nano pompon-shaped molybdenum sulfide/wood-based carbon porous electrode material and preparation method and application thereof | |
| CN113832478B (en) | Preparation method of high-current oxygen evolution reaction electrocatalyst with three-dimensional heterostructure | |
| CN111203231A (en) | Indium zinc sulfide/bismuth vanadate composite material and preparation method and application thereof | |
| Qian et al. | Recent progress of metal-organic framework-derived composites: Synthesis and their energy conversion applications | |
| CN113737218B (en) | Copper-based graphene aerogel composite catalyst, gas diffusion electrode and application | |
| CN111151275B (en) | MoS 2 /Mo 2 C Complex, MoS 2 /Mo 2 C/CdS composite material and preparation method and application thereof | |
| CN109395759B (en) | Fe with core-shell structure3C nano particle and preparation method and application thereof | |
| CN113663705B (en) | Lanthanum vanadate/graphite phase carbon nitride composite material and preparation method and application thereof | |
| Gui et al. | Nitrogen-doped porous carbon nanosheets as a robust catalyst for tunable CO 2 electroreduction to syngas | |
| CN114262901B (en) | Application of cuprous bromide in electrocatalytic decomposition of water | |
| CN110876950A (en) | Composite material containing metal hydroxide, preparation method and application thereof | |
| Jia et al. | Multicomponent catalyst design for CO 2/N 2/NO x electroreduction | |
| CN111804317A (en) | Method for directly growing high-density cobalt phosphide nano-wire electrocatalyst on conductive substrate and application thereof | |
| CN108855218B (en) | Preparation method for vacuum-packaged in-situ self-reaction synthesized multi-modified graphite-phase carbon nitride-loaded titanium dioxide | |
| CN114774983B (en) | Ultra-small Ru nanocluster supported on MoO 3-x Double-function composite material of nano belt and preparation method and application thereof | |
| CN114471624B (en) | NiSe 2 /Mn 0.3 Cd 0.7 S heterojunction photocatalyst, and in-situ synthesis method and application thereof | |
| Lu et al. | Electrocatalytic CO2 Reduction to Ethylene: From Advanced Catalyst Design to Industrial Applications | |
| CN115304055A (en) | Method for recovering polyethylene waste plastics and carbon nano tube prepared by method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |